Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Highly Preorganized Ligand 1,10-Phenanthroline-2,9-dicarboxylic Acid for the Selective Recovery of Uranium from Seawater in the Presence of Competing Vanadium Species

Abstract

Studies of the complexation of new promising ligands with uranyl (UO22+) and other seawater cations can aid the development of more efficient, selective, and robust sorbents for the recovery of uranium from seawater. Here, we propose that the ligand design principles based on structural preorganization can be successfully applied to obtain a dramatic enhancement in UO22+ ion binding affinity and selectivity. This concept is exemplified through the investigation of the com-plexes of UO22+, VO2+, and VO2+ with the highly preorganized ligand PDA (1,10-phenanthroline-2,9-dicarboxylic acid) using a combination of fluores-cence and absorbance techniques, along with den-sity functional theory (DFT) calculations. Moreover, the measured stability constant value, log K1, of 16.5 for the UO22+/PDA complex is very high compared to uranyl complexes with other dicarboxylic ligands. Moreover, PDA exhibits strong selectivity for uranyl over vanadium ions, since the determined sta-bility constant values of the PDA complexes of the vanadium ions are quite low (V(IV) log K1 = 7.4, V(V) = 7.3). Finally, the structures of the corresponding UO22+, VO2+, and VO2+ complexes with PDA were identified by systematic DFT calculations, and helped to interpret the stronger binding affinity for uranium over the vanadium ions. Due to its high chemical stability, selectivity, andmore » structural preor-ganization for UO22+ complexation, PDA is a very promising candidate that can be potentially used in the development of novel adsorbent materials for the selective extraction of uranium from sea-water.« less

Authors:
 [1];  [2];  [2];  [2];  [1]
+ Show Author Affiliations
  1. Univ. of North Carolina Wilmington, NC (United States). Dept. of Chemistry and Biochemistry
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Nuclear Energy (NE)
OSTI Identifier:
1329747
Grant/Contract Number:  
AC05-00OR22725; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 55; Journal Issue: 20; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS

Citation Formats

Lashley, Mark A., Ivanov, Alexander S., Bryantsev, Vyacheslav S., Dai, Sheng, and Hancock, Robert D. Highly Preorganized Ligand 1,10-Phenanthroline-2,9-dicarboxylic Acid for the Selective Recovery of Uranium from Seawater in the Presence of Competing Vanadium Species. United States: N. p., 2016. Web. doi:10.1021/acs.inorgchem.6b02234.
Copy to clipboard
Lashley, Mark A., Ivanov, Alexander S., Bryantsev, Vyacheslav S., Dai, Sheng, & Hancock, Robert D. Highly Preorganized Ligand 1,10-Phenanthroline-2,9-dicarboxylic Acid for the Selective Recovery of Uranium from Seawater in the Presence of Competing Vanadium Species. United States. https://doi.org/10.1021/acs.inorgchem.6b02234
Copy to clipboard
Lashley, Mark A., Ivanov, Alexander S., Bryantsev, Vyacheslav S., Dai, Sheng, and Hancock, Robert D. Fri . "Highly Preorganized Ligand 1,10-Phenanthroline-2,9-dicarboxylic Acid for the Selective Recovery of Uranium from Seawater in the Presence of Competing Vanadium Species". United States. https://doi.org/10.1021/acs.inorgchem.6b02234. https://www.osti.gov/servlets/purl/1329747.
Copy to clipboard
@article{osti_1329747,
title = {Highly Preorganized Ligand 1,10-Phenanthroline-2,9-dicarboxylic Acid for the Selective Recovery of Uranium from Seawater in the Presence of Competing Vanadium Species},
author = {Lashley, Mark A. and Ivanov, Alexander S. and Bryantsev, Vyacheslav S. and Dai, Sheng and Hancock, Robert D.},
abstractNote = {Studies of the complexation of new promising ligands with uranyl (UO22+) and other seawater cations can aid the development of more efficient, selective, and robust sorbents for the recovery of uranium from seawater. Here, we propose that the ligand design principles based on structural preorganization can be successfully applied to obtain a dramatic enhancement in UO22+ ion binding affinity and selectivity. This concept is exemplified through the investigation of the com-plexes of UO22+, VO2+, and VO2+ with the highly preorganized ligand PDA (1,10-phenanthroline-2,9-dicarboxylic acid) using a combination of fluores-cence and absorbance techniques, along with den-sity functional theory (DFT) calculations. Moreover, the measured stability constant value, log K1, of 16.5 for the UO22+/PDA complex is very high compared to uranyl complexes with other dicarboxylic ligands. Moreover, PDA exhibits strong selectivity for uranyl over vanadium ions, since the determined sta-bility constant values of the PDA complexes of the vanadium ions are quite low (V(IV) log K1 = 7.4, V(V) = 7.3). Finally, the structures of the corresponding UO22+, VO2+, and VO2+ complexes with PDA were identified by systematic DFT calculations, and helped to interpret the stronger binding affinity for uranium over the vanadium ions. Due to its high chemical stability, selectivity, and structural preor-ganization for UO22+ complexation, PDA is a very promising candidate that can be potentially used in the development of novel adsorbent materials for the selective extraction of uranium from sea-water.},
doi = {10.1021/acs.inorgchem.6b02234},
journal = {Inorganic Chemistry},
number = 20,
volume = 55,
place = {United States},
year = {Fri Sep 30 00:00:00 EDT 2016},
month = {Fri Sep 30 00:00:00 EDT 2016}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.inorgchem.6b02234
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 39 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: Ligands discussed in this paper.
All figures and tables (16 total)
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Seven chemical separations to change the world
journal, April 2016

  • Sholl, David S.; Lively, Ryan P.
  • Nature, Vol. 532, Issue 7600
  • DOI: 10.1038/532435a

Present Status of Study on Extraction of Uranium from Sea Water
journal, January 1984

Current status of adsorbent for metal ions with radiation grafting and crosslinking techniques
journal, July 2005

  • Seko, Noriaki; Tamada, Masao; Yoshii, Fumio
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 236, Issue 1-4
  • DOI: 10.1016/j.nimb.2005.03.244

Recovery of Uranium from Seawater: A Review of Current Status and Future Research Needs
journal, January 2013

Aquaculture of Uranium in Seawater by a Fabric-Adsorbent Submerged System
journal, November 2003

  • Seko, Noriaki; Katakai, Akio; Hasegawa, Shin
  • Nuclear Technology, Vol. 144, Issue 2
  • DOI: 10.13182/NT03-2

Extraction of uranium from seawater by polymer-bound macrocyclic hexaketone
journal, August 1979

  • Tabushi, Iwao; Kobuke, Yoshiaki; Nishiya, Takako
  • Nature, Vol. 280, Issue 5724
  • DOI: 10.1038/280665a0

Cost Estimation of Uranium Recovery from Seawater with System of Braid Type Adsorbent [モール状捕集システムによる海水ウラン捕集のコスト試算]
journal, January 2006

  • Tamada, Masao; Seko, Noriaki; Kasai, Noboru
  • Transactions of the Atomic Energy Society of Japan, Vol. 5, Issue 4
  • DOI: 10.3327/taesj2002.5.358

Amidoximes as ligand functionalities for braided polymeric materials for the recovery of uranium from seawater
journal, April 2016

Sequestering uranium from seawater: binding strength and modes of uranyl complexes with glutarimidedioxime
journal, January 2012

  • Tian, Guoxin; Teat, Simon J.; Zhang, Zhiyong
  • Dalton Transactions, Vol. 41, Issue 38
  • DOI: 10.1039/c2dt30978e

Thermodynamic studies of U(vi) complexation with glutardiamidoxime for sequestration of uranium from seawater
journal, January 2013

  • Tian, Guoxin; Teat, Simon J.; Rao, Linfeng
  • Dalton Transactions, Vol. 42, Issue 16
  • DOI: 10.1039/c3dt32940b

Quantifying the binding strength of U( vi ) with phthalimidedioxime in comparison with glutarimidedioxime
journal, January 2014

  • Sun, Xiaoqi; Tian, Guoxin; Xu, Chao
  • Dalton Trans., Vol. 43, Issue 2
  • DOI: 10.1039/C3DT52206G

Complexation of glutarimidedioxime with Fe(iii), Cu(ii), Pb(ii), and Ni(ii), the competing ions for the sequestration of U(vi) from seawater
journal, January 2013

  • Sun, Xiaoqi; Xu, Chao; Tian, Guoxin
  • Dalton Transactions, Vol. 42, Issue 40
  • DOI: 10.1039/c3dt51767e

Uptake of Uranium from Seawater by Amidoxime-Based Polymeric Adsorbent: Field Experiments, Modeling, and Updated Economic Assessment
journal, March 2014

  • Kim, Jungseung; Tsouris, Costas; Oyola, Yatsandra
  • Industrial & Engineering Chemistry Research, Vol. 53, Issue 14
  • DOI: 10.1021/ie4039828

Vanadium speciation and cycling in coastal waters
journal, December 2009

Vanadium behaviour in the global ocean and in the Mediterranean sea
journal, May 1987

Vanadyl in natural waters: Adsorption and hydrolysis promote oxygenation
journal, January 1989

Fractional Elution and Determination of Uranium and Vanadium Adsorbed on Amidoxime Fiber from Seawater.
journal, January 2000

  • Suzuki, Toshihiro; Saito, Kyoichi; Sugo, Takanobu
  • Analytical Sciences, Vol. 16, Issue 4
  • DOI: 10.2116/analsci.16.429

Theoretical study of the coordination behavior of formate and formamidoximate with dioxovanadium( v ) cation: implications for selectivity towards uranyl
journal, January 2015

  • Mehio, Nada; Johnson, J. Casey; Dai, Sheng
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 47
  • DOI: 10.1039/C5CP06165B

Theoretical Study of Oxovanadium(IV) Complexation with Formamidoximate: Implications for the Design of Uranyl-Selective Adsorbents
journal, December 2015

  • Mehio, Nada; Ivanov, Alexander S.; Ladshaw, Austin P.
  • Industrial & Engineering Chemistry Research, Vol. 55, Issue 15
  • DOI: 10.1021/acs.iecr.5b03398

Structural and spectroscopic studies of a rare non-oxido V( v ) complex crystallized from aqueous solution
journal, January 2016

  • Leggett, C. J.; Parker, B. F.; Teat, S. J.
  • Chemical Science, Vol. 7, Issue 4
  • DOI: 10.1039/C5SC03958D

Preparation of hydrophilic amidoxime fibers by cografting acrylonitrile and methacrylic acid from an optimized monomer composition
journal, October 2000

  • Kawai, Tomomi; Saito, Kyoichi; Sugita, Kazuyuki
  • Radiation Physics and Chemistry, Vol. 59, Issue 4, p. 405-411
  • DOI: 10.1016/S0969-806X(00)00298-X

Design of complexes between synthetic hosts and organic guests
journal, January 1978

  • Cram, Donald J.; Cram, Jane M.
  • Accounts of Chemical Research, Vol. 11, Issue 1
  • DOI: 10.1021/ar50121a002

Solvent extraction: the coordination chemistry behind extractive metallurgy
journal, January 2014

  • Wilson, A. Matthew; Bailey, Phillip J.; Tasker, Peter A.
  • Chem. Soc. Rev., Vol. 43, Issue 1
  • DOI: 10.1039/C3CS60275C

Challenges to achievement of metal sustainability in our high-tech society
journal, January 2014

  • Izatt, Reed M.; Izatt, Steven R.; Bruening, Ronald L.
  • Chem. Soc. Rev., Vol. 43, Issue 8
  • DOI: 10.1039/c3cs60440c

Molecular design of calixarene-based uranophiles which exhibit remarkably high stability and selectivity
journal, October 1987

  • Shinkai, Seiji; Koreishi, Hiroshi; Ueda, Kaori
  • Journal of the American Chemical Society, Vol. 109, Issue 21
  • DOI: 10.1021/ja00255a023

Crystal Structure of a Uranyl/p-tert-Butylcalix[5]arene Complex
journal, January 1997

  • Thuéry, Pierre; Nierlich, Martine
  • Journal of Inclusion Phenomena and Molecular Recognition in Chemistry, Vol. 27, Issue 1, p. 13-20
  • DOI: 10.1023/A:1007938218723

Encapsulation of the uranyl dication
journal, January 2010

  • Beer, Stephan; Berryman, Orion B.; Ajami, Dariush
  • Chemical Science, Vol. 1, Issue 1
  • DOI: 10.1039/c0sc00116c

A protein engineered to bind uranyl selectively and with femtomolar affinity
journal, January 2014

  • Zhou, Lu; Bosscher, Mike; Zhang, Changsheng
  • Nature Chemistry, Vol. 6, Issue 3
  • DOI: 10.1038/nchem.1856

Chelate ring size and metal ion selection. The basis of selectivity for metal ions in open-chain ligands and macrocycles
journal, August 1992

  • Hancock, Robert D.
  • Journal of Chemical Education, Vol. 69, Issue 8
  • DOI: 10.1021/ed069p615

Ligand design for selective complexation of metal ions in aqueous solution
journal, December 1989

  • Hancock, Robert D.; Martell, Arthur E.
  • Chemical Reviews, Vol. 89, Issue 8
  • DOI: 10.1021/cr00098a011

Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976

Unusual Metal Ion Selectivities of the Highly Preorganized Tetradentrate Ligand 1,10-Phenanthroline-2,9-dicarboxamide: A Thermodynamic and Fluorescence Study
journal, September 2011

  • Merrill, Danielle; Harrington, James M.; Lee, Hee-Seung
  • Inorganic Chemistry, Vol. 50, Issue 17
  • DOI: 10.1021/ic200905f

Metal Ion Complexing Properties of the Highly Preorganized Ligand 2,9-bis(Hydroxymethyl)-1,10-phenanthroline: A Crystallographic and Thermodynamic Study
journal, November 2008

  • Gephart, Raymond T.; Williams, Neil J.; Reibenspies, Joseph H.
  • Inorganic Chemistry, Vol. 47, Issue 22
  • DOI: 10.1021/ic8008656

Complexation of Metal Ions of Higher Charge by the Highly Preorganized Tetradentate Ligand 2,9-Bis(hydroxymethyl)-1,10-Phenanthroline. A Crystallographic and Thermodynamic Study
journal, September 2009

  • Gephart, Raymond T.; Williams, Neil J.; Reibenspies, Joseph H.
  • Inorganic Chemistry, Vol. 48, Issue 17
  • DOI: 10.1021/ic900650d

Complexes of the highly preorganized ligand PDALC (2,9-bis(hydroxymethyl)-1,10-phenanthroline) with trivalent lanthanides. A thermodynamic and crystallographic study
journal, November 2010

  • Williams, Neil J.; Ballance, Daniel G.; Reibenspies, Joseph H.
  • Inorganica Chimica Acta, Vol. 363, Issue 14
  • DOI: 10.1016/j.ica.2010.05.023

Enhanced Metal Ion Selectivity of 2,9-Di-(pyrid-2-yl)-1,10-phenanthroline and Its Use as a Fluorescent Sensor for Cadmium(II)
journal, January 2008

  • Cockrell, Gregory M.; Zhang, Gang; VanDerveer, Donald G.
  • Journal of the American Chemical Society, Vol. 130, Issue 4
  • DOI: 10.1021/ja077141m

Synthesis of some 2,9-disubstituted-1,10-phenanthrolines
journal, May 1981

  • Chandler, Christopher J.; Deady, Leslie W.; Reiss, James A.
  • Journal of Heterocyclic Chemistry, Vol. 18, Issue 3
  • DOI: 10.1002/jhet.5570180332

Relativistic and correlation effects for element 105 (hahnium, Ha): a comparative study of M and MO (M = Nb, Ta, Ha) using energy-adjusted ab initio pseudopotentials
journal, June 1993

  • Dolg, Michael; Stoll, Hermann; Preuss, Heinzwerner
  • The Journal of Physical Chemistry, Vol. 97, Issue 22
  • DOI: 10.1021/j100124a012

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
  • DOI: 10.1063/1.464913

Energy Levels and Thermodynamic Functions for Molecules with Internal Rotation I. Rigid Frame with Attached Tops
journal, July 1942

  • Pitzer, Kenneth S.; Gwinn, William D.
  • The Journal of Chemical Physics, Vol. 10, Issue 7
  • DOI: 10.1063/1.1723744

Identification and treatment of internal rotation in normal mode vibrational analysis
journal, February 1998

  • Ayala, Philippe Y.; Schlegel, H. Bernhard
  • The Journal of Chemical Physics, Vol. 108, Issue 6
  • DOI: 10.1063/1.475616

Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions
journal, May 2009

  • Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G.
  • The Journal of Physical Chemistry B, Vol. 113, Issue 18, p. 6378-6396
  • DOI: 10.1021/jp810292n

Predicting Stability Constants for Uranyl Complexes Using Density Functional Theory
journal, March 2015

Assessing ligand selectivity for uranium over vanadium ions to aid in the discovery of superior adsorbents for extraction of UO 2 2+ from seawater
journal, January 2016

  • Ivanov, Alexander S.; Bryantsev, Vyacheslav S.
  • Dalton Transactions, Vol. 45, Issue 26
  • DOI: 10.1039/C6DT01752E

Natural hybrid orbitals
journal, September 1980

  • Foster, J. P.; Weinhold, F.
  • Journal of the American Chemical Society, Vol. 102, Issue 24
  • DOI: 10.1021/ja00544a007

Topological analysis of electron density distribution taken from a pseudopotential calculation
journal, February 1997

All-Electron Scalar Relativistic Basis Sets for Third-Row Transition Metal Atoms
journal, May 2008

  • Pantazis, Dimitrios A.; Chen, Xian-Yang; Landis, Clark R.
  • Journal of Chemical Theory and Computation, Vol. 4, Issue 6
  • DOI: 10.1021/ct800047t

Alternative Alkaline Conditioning of Amidoxime Based Adsorbent for Uranium Extraction from Seawater
journal, October 2015

  • Das, S.; Liao, W. -P.; Flicker Byers, M.
  • Industrial & Engineering Chemistry Research, Vol. 55, Issue 15
  • DOI: 10.1021/acs.iecr.5b03210

Adsorption of UO2+2 by polyethylene adsorbents with amidoxime, carboxyl, and amidoxime/carboxyl group
journal, February 2000

Theoretical Insights on the Interaction of Uranium with Amidoxime and Carboxyl Groups
journal, August 2014

  • Wang, Cong-Zhi; Lan, Jian-Hui; Wu, Qun-Yan
  • Inorganic Chemistry, Vol. 53, Issue 18
  • DOI: 10.1021/ic500202g

Stability Constants of Some Uranyl Complexes
journal, June 1968

  • Ramamoorthy, S.; Santappa, M.
  • Bulletin of the Chemical Society of Japan, Vol. 41, Issue 6
  • DOI: 10.1246/bcsj.41.1330

Hyperquad simulation and speciation (HySS): a utility program for the investigation of equilibria involving soluble and partially soluble species
journal, April 1999

Principles of Fluorescence Spectroscopy
book, January 2006

Scientific Basis for Efficient Extraction of Uranium from Seawater. I: Understanding the Chemical Speciation of Uranium under Seawater Conditions
journal, December 2015

  • Endrizzi, Francesco; Leggett, Christina J.; Rao, Linfeng
  • Industrial & Engineering Chemistry Research, Vol. 55, Issue 15
  • DOI: 10.1021/acs.iecr.5b03679
    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Strategic Design and Utilization of Molecular Flexibility for Straddling the Application of Organic Superbases: A DFT Study
    journal, January 2018

    • Singh, Ajeet; Ojha, Animesh K.; Jang, Hyun Myung
    • ChemistrySelect, Vol. 3, Issue 2
    • DOI: 10.1002/slct.201702912

    The impact of alicyclic substituents on the extraction ability of new family of 1,10-phenanthroline-2,9-diamides
    journal, January 2020

    • Lemport, Pavel S.; Matveev, Petr I.; Yatsenko, Alexander V.
    • RSC Advances, Vol. 10, Issue 44
    • DOI: 10.1039/d0ra05182a

    A highly efficient uranium grabber derived from acrylic fiber for extracting uranium from seawater
    journal, January 2020

    • Pan, Horng-Bin; Wai, Chien M.; Kuo, Li-Jung
    • Dalton Transactions, Vol. 49, Issue 9
    • DOI: 10.1039/c9dt04562g
      Sort by:
      [ × clear filter / sort ]

      Figures / Tables found in this record:

      Figure 1 (p. 2)figure
      Scheme 1 (p. 2)figure
      Scheme 2 (p. 3)figure
      Scheme 3 (p. 4)figure
      Figure 2 (p. 5)figure
      Table 1 (p. 5)table
      Figure 3 (p. 7)figure
      Table 2 (p. 8)table
      Figure 4 (p. 9)figure
      Figure 5 (p. 9)figure
      Table 3 (p. 9)table
      Table 4 (p. 9)table
      Figure 6 (p. 11)figure
      Table 5 (p. 11)table
      Table 6 (p. 12)table
      Figure 7 (p. 13)figure
        [ × clear filter / sort ]
        Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

        Similar Records in DOE PAGES and OSTI.GOV collections: